Title: Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers

Abstract: We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller-diameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios ($\sigma=0.16-0.66$) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are non-additive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio we control the extent of non-additivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios we tune the system from a mobile small-particle phase ($\sigma<0.24$), to an interstitial solid ($0.24<\sigma<0.33$), to a disordered glass ($\sigma>0.33$). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice's capacity for small-particle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D non-additive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.